Compounded mineral oil



Patented Aug. 20; 1940 UNITED STATES 2,211,972 COMPOUNDED MINERAL 01L Elmslie W. Gardiner and George H. Dcnison, Jr.,

Berkeley, Calif.,

assignors to Standard Oil Company of California, San Francisco, Calif., a corporation of Delaware No Drawings 23 Claims.

This invention relates to new and useful compositions of matter and involves more particularly a composition comprising a hydrocarbon oil and an aluminum phenate of high molecular weight 5 phenols.

The production of improved hydrocarbon oils and particularly of lubricating oils having desired characteristics has been the subject of extensive research and investigation in recent years. Generally speaking, the compounding of hydrocarbon voils to obtain desired characteristics involves empirical phenomena, and the action of untested types of compounding agents cannot be predicted.

A characteristic which has been the subject of 'intensiveinvestigation is the tendency of hydrocarbon oils to deteriorate or partially decompose when subjected to high temperatures. This deterioration is evidenced by the deposition of adhesive deposits on hot metallic surfaces over which the hydrocarbon oil may flow. It is important that resistance to such deterioration be imparted to hydrocarbon oils, particularly to lubricating oils, in order that such compositions may be relatively free from the tendency to form such deposits even under high temperatures and severe operating conditions. this type of deterioration during lubrication of internal combustion engines, such as engines ofr the Diesel type, is the tendency of the oil to cause or permit the sticking of piston rings. Compounds which render hydrocarbon oils more resistant to deterioration by heat at high temperature levels usually, although not always, impart to the oil the ability to inhibit piston ring sticking in internal combustion engines and permit longer periods of operation of such engines without the necessity of major overhauls heretofore occasioned by stuck piston rings.

It has been discovered that dispersion of aluminum phenates in hydrocarbon oils, such as mineral lubricating oil, imparts new and unpredictable properties thereto. These new properties render the compounded oil particularly useful for various purposes. For example, aluminum phenates like aluminum lauryl phenates, aluminum cetyl phenates, aluminum heptyl phenates are capable of inhibiting piston ring sticking when incorporated in 50 crank-case lubricants for internal combustion engines such as Diesel engines.

In general, it has been discovered that the new compositions herein disclosed are more stable to heat than is the hydrocarbon oil from which the 5 compositions are compounded. The aluminum phenates are capable of imparting to mineral lubricating oils the property of resistance to sludge formation and/or to the deposition of lacquer or gumlike materials on metal surfaces at 00 high temperatures such as 425 to 550 F. en-

A direct result of aluminum di-amyl phenate and Application October 4, 1938, erial No. 233,329

countered in the ring Thenew compositions of this invention are, therefore, particularly useful where resistance to heat is an important factor. In addition to having outstanding advantages as a lubricant for pistons and piston rings of internal combustion engines, the present hydrocarbon compositions are useful as heat transfer fluids where it may be desirable to inhibit or prevent the formation of adepositonthe metal surface from or to which heat is being. conveyed.

It has also been discovered that aluminum phenates have a combinationof propertiesparticularly desirable in compounded lubricating oils; namely, both the ability to inhibit piston ring sticking and non-corrosivity of the compounded oil as respects its chemical action on bearing metals such as cadmium-silver alloys. Although various compounded oils are known which are capable of inhibiting piston ring sticking, the discovery of specific compounding agents capable of imparting the above combination of properties to hydrocarbon oils represents an unobvious and important contribution.

specific examples of aluminum phenates which may be added to hydrocarbon oils such as mineral lubricating oils to provide a new composition of matter of the type hereininvolved,comprise aluminum amyl phenates, aluminum hexylphenates,aluminum heptyl phenates, aluminum octyl phenates, aluminum nonyl phenates, aluminum decyl phenates, aluminum undecyl phenates, aluminum dodecyl (lauryl) phenates, aluminum cetyl phenates and aluminum lauryl or cetyl cresylates.

Phenates other than alkyl phenates may be utilized. The phenates of this invention are belt zone of Diesel engines.

preferably formed from high molecular weight alkyl phenols of the type formula i on U in which R is an alkyl radical containing at least 5 carbon atoms. Although alkyl substituents in the phenolic radical of the present compounds are preferred, oil-soluble aluminum phenates of other substituted phenols may be substituted therefor. The invention does not preclude substitution of alkyl, aryl, alkaryl, aralkyl and cyclic nonbenzenoid groups, either alone or together with an alkyl group in the aromatic nucleus to which-the phenolic hydroxyl group is'directly attachedn In general, the phenolic radical of the aluminum phenates should contain more than 10 carbon atoms and preferably It is to be understood that the term high molecular weight phenols is intended to designate phenols having a molecular weight greater than ap- 16 or more carbon atoms.

" of glacial acetic acid.

temperature.

proximately 100. Compounds containing one or more alkyl groups are contemplated. For example, either mono-alkyl phenolic or di-alkyl phenolic radicals may be utilized in the present invention.

To guide those skilled in the art in the preparation of the compositions of this invention, the following specific examples are submitted:

Example 1.-An alkyl phenol desirable for present purposes may be obtained as follows: A mixture of phenol and a butene polymer having an apparent molecular weight of, 194 and obtained by polymerization of a mixture of butenes containing butene-1, butene-2, and iso-butene was prepared. To this mixture, containing 237 grams of phenol and 500 grams of the above mentioned butene polymers, 140 cubic centimeters of 94% sulfuric acid was added slowly with agitation. The temperature was kept below 65 F. during the addition of the acid. The mixture was agitated for two hours after the addition of acid was completed and permitted to come to room The reaction product was then diluted with an equal volume of water and placed in a sealed autoclave where it was heated at 350 F. for an hour with agitation. The product was washed with water, 5% sodium carbonate solution and again with water in order to free it of sulfuric acid, sulfonates and unreacted phenol. A 93% yield of high molecular weight water-insoluble alkyl phenol having an acetyl number of 181 was obtained.

Example 2.511 grams of crude cresylic acid, 900 grams of olefine polymers containing an average of 14 carbon atoms per molecule and 475 grams of 98% sulfuric acid were,utilized in preparing an alkylated cresol. These ingredients were combined and treated in the manner described above for preparation of cetyl phenol. The product was vacuum-distilled at 10 mm. and a 50 to cut of an alkyl phenol obtained, which had a molecular weight of 291.

It is to be understood that the above examples are given by way of illustration only and that other condensation reactions utilizing alcohols, alkyl chlorides and the like rather than olefines may be adopted as a starting material for introducing the alkyl group into the aromatic nucleus. Also other known condensation agents, such as aluminum chloride, zinc chloride, etc., may be adopted for eflecting the alkylation reaction. A mixture of sulfuric and glacial acetic acids may be used with advantage as a condensing agent. A suitable mixture comprises parts by weight 98% H2804 to 60 parts by weight The presence of the acetic acid facilitates temperature control and gives a softer, easier handled reaction product.

The following comprises an illustrative example of a method for obtaining the aluminum phenate of this invention:

A mixture of 4 grams of aluminum metal, 45 grams of an alkylated phenol averaging approximately cetyl phenol and a crystal of iodine were heated at a temperature above approximately 340 F. for about four hours or until gas evolution had apparently ceased. The alkylated phenol is preferably one prepared from butene polymers, as above described. The gas formed comprised hydrogen and was removed as the re- .action progressed. The product remaining in the reaction zone was dissolved in petroleum ether and filt red. The filtrate, after removal of petroleum ether, showed an ash of 7.46%. This corresponds to about 99% yield calculated on (cetyl phenate), i. e.,

The aluminum phenates prepared by the above type of process comprise a basic phenate, that is, an aluminum phenate containing insuflicient phenol to satisfy the three valences of the aluminum. Aluminum di-phenates comprise a preferred species of the invention. The normal salt may be made by proper control of the quantity of the alkyl phenol and operating condition 'in the reaction zone. A large excess of the phenol produces phenates containing a greater proportion of the phenolic radical.

The proportion of aluminum phenates added to mineral lubricating oils may vary widely, depending upon the uses involved and the properties desired. As little as 0.1% by weight of the phenate gives measurable improvements, although from approximately 0.25 to approximately 2% phenate is preferred where the compounded oil is to be used as a crankcase lubricant for internal combustion engines. As much as 50% by weight of various of the phenates may be dissolved in mineral oil for the purpose of preparing a concentrate capable of dilution with lubricating oils and the like. Such concentrates comprise a convenient method of handling the phenates and may be usedas a compounding agent for lubricants in general, as well as for other purposes.

The advantages of the compounded mineral oil of this invention are illustrated by the following data:

- Same oil lus Western 01! 1% nlumi um Test s. a. E. 30 d! acid refined phenate) Hour: to cause ring sticking 30 90. Relatifcaconoslllmatd be 1 v I a opper-e armgs er am... e ow. 5b Cadmium-silver alloys i %)0. Relative ring slot carbon Excellent. Relative piston cleanliness .-do Good. Used oll inspection at time ring stuck:

(a) Vis. at 100 F (b) Vls. at 210 F (2) Neutralization No continuous at 1600 R. P. M. except for periodic shut-downs at 15-hour intervals for inspection; the jacket temperature was maintained at 345 F. and sump oil temperature at 220 F. The corrosion data given represent the loss of weight of metal from the bearings during runs with this type of engine under the above severe conditions.

Attention is directed to the fact that 1% aluminum phenate imparted to the mineral lubricating oil marked resistance to heat and sludging as shown by the fact that the life of the oil was tripled insofar as its ability to prevent piston ring sticking is concerned.-

The aluminum phenates of this invention may be added to the mineral oils containing other compounding ingredients, such as pour point depressors, oiliness agents, extreme pressure addition agents, corrosion inhibitors. blooming agents, compounds for increasing the viscosity index of the h drocarbon oil, etc. The invention I5 the preparation and application of the composition given, this has been doneby way of illustration only and with the intention that no limitation should be imposed on the invention thereby. It will be apparent to those skilled in the art that numerous modifications and variations of the illustrative examples may be effected in the practice of the invention which is of the scope of the claims appended hereto- We claim:

1. A composition of matter comprising an oil and more than approximately 0.1% of an aluminum phenate dissolved therein, said phenate containing a substituted phenolic radical having 1 more than 10 carbon atoms. I

2. A composition of matter comprising a hydrocarbon oil and more than approximately 0.1% of an aluminum phenate containing a radical of the type formula in which R is an alkyl group containing at least 5 carbon atoms.

3. A composition of matter comprising a hydrocarbon oil and more than approximately 0.1% of an aluminum phenate containing an aromatic nucleus having an alkyl group with at least 5 carbon atoms attached thereto.

4. A composition of matter comprising a hydrocarbon oil and more than approximately 0.1% of an aluminum phenate cleus having an alkyl attached thereto.

5. A composition of matter comprisinga'hydrocarbon oil and more than approximately 0.1% of an aluminum phenate containing an aromatic nucleus having an alkyl group with 16 carbon atoms attached thereto.

6. A lubricating composition comprising a mineral lubricating oil and an aluminum phenate dissolved therein in an amount'suillcient substantially to inhibit deterioration of said oil at elevated temperatures, said phenate containing a substituted phenolic radical having more than 10 carbon atoms. Y v

'Z. A lubricating compostion comprising a mineral lubricating oil and an aluminum phenate containing a radical of the type formula containing an aromatic nuin which R is an alkyl group containing at least 5 carbon atoms, said phenate being present in an amount suflicient substantially to inhibit deterioration of said oil at elevated temperatures.

8. A lubricating composition comprising a lubricating oil and an aluminum phenate containing an aromatic nucleus having 'analkyl group with at least 5 carbon atoms attached thereto, said group with 12 carbon atoms phenate being present in an amount suflicient substantially to inhibit deterioration of said oil at elevated temperatures.

-9. A lubricating composition comprising a mineral lubricating oil and an aluminum phenate containing an aromatic nucleus having an alkyl group with 12 carbon atoms attached thereto, said phenate being present in an amount suflicient substantially to inhibit deterioration of said oil at elevated temperatures.

10. A lubricating composition comprising a mineral lubricating oil and an aluminum phenate containing an aromatic nucleus having an alkyl group with 16 carbon atoms attached thereto, said phenate being present in an amount suflicient substantially to inhibit deterioration of said oil at elevated temperatures. 1

11. A composition of matter comprising a hydrocarbon oil and more than approximately 0.1% of a basic aluminum phenate.

12. A composition of matter comprising a hydrocarbon oil andmore than approximately 0.1% of an aluminum dl-phenate.

13. A composition of matter comprising a hydrocarbon oil and more than approximately 0.1% of a compound of the type formula in which R. is an alkyl group containing at least 5 carbon atoms.

14. A composition of matter comprising a hydrocarbon oil and more than approximately 0.1% of a compound 0! the formula CuHn nolic radical having a hydrocarbon substituent' in the aromatic nucleus selected from the class consisting of alkyl, aryl, alkaryl, aralkyl and cyclic non-benzenoid groups.

17. A liquid lubricating oil, as defined in claim than approximately phenate is a basic aluminum where R is an alkyl radical containing at least 5 carbon atoms. 20. A liquid lubricating oil, as defined in claim 16, in which the phenate is of the type formula where R is an alkyl group containing at least 5 carbon atoms 21. A liquid lubricating oil comprising a. hydrocarbon oil normally having the tendency to cause piston ring sticking in internal combustion engines, such as Diesel engines, and a small amount of an alkylated aluminum phenate having a phenolic radical containing more than ten carbon atoms, said phenate being present in the oil in an amount sufllcient' substantially to inhibit piston ring sticking.

22. A liquid lubricating ofl comprising a hydrocarbon oil normally having the tendency to cause piston ring sticking in internal combustion engines, such as Diesel engines, and a small amount of an alkylated aluminum phenate having an alkyl radical with at least ten carbon atoms, said phenate, being present in the oil in an amount sufllcient substantially to inhibit piston ring sticking.

23. A composition of matter comprising a hydrocarbon 011 containing from approximately 0.1% to 50% by weight of an aluminum phenate having a phenolic radical with more than approximately ten carbon atoms.

ELMSLIE W. GARDINER. GEORGE H. DENISON, Jn. 

